12
J.A. Balam-Villarreal et al. / Journal of Organometallic Chemistry 818 (2016) 7e14
values of the signals are expressed in mass/charge units (m/z),
followed by the relative intensity with reference to a 100% base
peak. Elemental analyses for carbon, hydrogen and sulfur atoms
were performed on a Perkin Elmer 2400 elemental 35 analyzer
using cystine as standard.
obtained. To this solution was then added, dropwise, a dichloro-
methane solution (5 mL) of O-ethyl ferrocenylthionoester
1
(0.5 mmol, 136.9 mg). The mixture reaction was stirred for 3 h at
room temperature, obtaining a deep purple solid. The solvent was
evaporated and the resulting crude was suspended in CH2Cl2 and
treated with PPh3 (0.5 mmol, 131.2 mg) at room temperature,
during 2 h. The solvent was evaporated and the precipitate ob-
tained was filtered and washed with hexane. The precipitate was
purified by column chromatography on neutral alumina (eluent;
hexane/CH2Cl2 1:1) to give 3a (304.5 mg, 90%). A similar procedure
for the preparation of 3a was followed to synthesize 3b, 3c and 3d.
The equipment used for irradiation with IR energy was created
by employing an empty cylindrical metal vessel in which an Osram
lamp (bulb model Thera-Therm, 250 W, 125 V) was inserted [22a].
This lamp is special short-wave IR lamp (IR-A) for use in body care
and wellness applications, with a maximum radiation at a wave-
length of about 1100 nm. The lamp instantly emits a full thermal
output as soon as it is switched on. For controlling the temperature,
a Digi-Sense variable-time power controller was used. This time
controller turned the output load on and off and then repeated the
cycle. All the reactions were performed in open atmosphere.
Microwave irradiation experiments were performed using a
Monowave 300 single-mode microwave reactor. The reaction
temperature is monitored by an internal fiber-optic (FO) tempera-
ture probe (ruby thermometer) protected by a borosilicate im-
mersion well inserted directly into the reaction mixture. Reaction
times refer to the hold time at the desired set temperature and not
to total irradiation time. A hydraulic sensor integrated in the
swiveling cover of the instrument performs pressure sensing. The
reusable 10 mL Pyrex vial is sealed with PEEK snap caps and
standard PTFE coated silicone septa. Reaction cooling is performed
by compressed air automatically after the heating period has
elapsed. All the reactions were performed in open atmosphere.
The reactions conducted under ultrasound irradiation were
carried out in a flask, suspended into the ultrasonic bath (Bransonic
2510R-MTH, 42 KHz frequency, 550 W power). A Digi-Sense vari-
able-time power controller was used for controlling the tempera-
ture. All the reactions were performed in open atmosphere.
3a. C31H28ClFeOPdPS. 90%, mp 162e164 ꢁC (dec). IRn
(KBr,
max
cmꢀ1): 3074, 2965, 2925 (CeH), 1257 (C]S). MS-FABþ m/z (rel.
intensity %) 677 [Mþ] (5), 642 [MþeCl] (26), 523 [Mþe(C6H5)2 ]. 1H
NMR (CDCl3, ppm):
d 1.54 [t, 3H, CH3], 3.88 [br s, 6H, CH (Cp sub)
and CH Cp], 4.37 [m, 1H, CH (Cp sub)], 4.65 (m, 3H, CH2O and CH (Cp
Sub)], 7.42 (br s, 9H, CHarom m, p), 7.76 (br s, 6H, CHarom o). 13C NMR
(CDCl3, ppm): d 14.3 [CH3], 67.0 [ CH (Cp sub)], 70.9 [CH2O], 72.4 [CH
(Cp sub)] 72.9 [CH, Cp], 81.2 [CH (Cp sub)], 89.5 [ Cipso C(S)], 95.5 [
Cipso Pd], 128.3 [d, JC-P ¼ 10.4 Hz, CHarom m], 130.7 [CHarom p], 134.9
[d, JC-P ¼ 47.4 Hz, CipsoP], 135.2 [d, JC-P ¼ 12.7 Hz, CHarom o], 224.2
[C(S)OEt]. 31P NMR (CDCl3, ppm):
d 35.6. Elemental analysis (%):
calcd for C31H28ClFeOPdPS C, 54.94; H, 4.16; S, 4.73; found: C, 53.89;
H, 3.96; S, 4.71.
3b. C34H34ClFeOPdSP. Deep purple solid, 90%, mp 148e151 ꢁC
(dec). IRnmax (KBr, cmꢀ1): 3061, 2924, (CeH). 1258 (C]S). MS-FABþ
m/z (rel. intensity %) 719 [Mþ] (5), 683 [MþeCl], 415 [MþeP(o-
tolyl)3]. 1H NMR (CDCl3, ppm):
d 1.54 [t, 3H, CH3CH2O], 1.68 [s, 3H,
CH3 P(o-tolyl)3], 2.15 [s, 3H, CH3 P(o-tolyl)3], 3.36 [s, 3H, CH3 P(o-
tolyl)3], 3.74 [s, 5H, CH Cp], 3.82 (s, 1H, CH (Cp sub)], 4.38 [s, 1H, CH
(Cp sub)], 4.67 [br s, 3H, eCH2O, CH (Cp sub)], 7.08e7.57 (m, 9H, CH
arom), 8.64 (dd, 3H, CHarom JH-P ¼ 18 Hz). 13C NMR (CDCl3, ppm):
d
15.4 [CH3CH2Oe], 23.1 [CH3, JC-P ¼ 9.2 Hz], 23.8 [CH3, JC-P ¼ 9.2 Hz],
4.2. Structure determination by X-ray crystallography
25.3 [CH3, JC-P ¼ 9.2 Hz], 66. 7 [CH, (Cp sub)], 70.7 [CH2eO], 72.1[CH,
(Cp sub)], 72.5 [CH, Cp], 80.5 [CH, (Cp sub)] 89.1 [Cipso-C(S)], 94.7
[Cipso-Pd)], 125.3 [CHarom], 130.4 (CHarom), 131.0(CHarom), 132.9
(CHarom, JC-P ¼ 5.25 Hz), 143.7 (CipsoP), 144.7 (CipsoCH3 JC-P ¼ 30 Hz),
Suitable X-ray quality crystal of 3b was grown by slow evapo-
ration of chloroform at room temperature. A crystal of 3b was
mounted on a glass fiber at room temperature, and then placed on a
Bruker Smart Apex CCD diffractometer, equipped with Mo-Ka ra-
Table 5
diation; decay was negligible in both cases. Details of crystallo-
graphic data collected on compounds 3b is provided in Table 5.
Systematic absences and intensity statistics were used in space
group determination. The structure was solved using direct
methods [31]. Anisotropic structure refinements were achieved
using full matrix, least-squares technique on all non-hydrogen
atoms. All hydrogen atoms were placed in idealized positions,
based on hybridization, with isotropic thermal parameters fixed at
1.2 times the value of the attached atom. Structure solutions and
refinements were performed using SHELXTL V6.10 [32]. The
experimental and refinement details of the X-ray crystallographic
structure of compound 3b can be obtained free of charge from the
uk), reference code 952478.
X-ray data collection and structure refinement details for 3b.
3b
Formula
C35H36Cl3FeOPPdS
804.27
0.32 ꢂ 0.21 ꢂ 0.14
Monoclinic
P21/n
MW gꢀ1 molꢀ1
Crystal size (mm3)
Crystal system
Space group
a/Å
10.128(1)
b/Å
23.854(1)
c/Å
a
14.183(1)
90
93.078(1)
90
3421.6(4)
4
1.561
1.67 to 25.39
ꢀ12 ꢃ h ꢃ 12
ꢀ28 ꢃ k ꢃ 28
ꢀ17 ꢃ l ꢃ 17
27882
/(ꢁ)
/(ꢁ)
b
g
/(ꢁ)
Volume/Å3
Z
dc/Mg mꢀ3
ꢁ
Q
/
4.3. Synthesis of fischer ethoxy ferrocenyl carbene complex and O-
ethyl ferrocenylthionoester (1)
Index Ranges
The preparation of these compounds was carried out using the
methodology previously described elsewhere [14,22].
Reflections collected
Independent reflections
Data/parameters
6274 [R(int) ¼ 0.0535]
6274/431
Final R indices
[I > 2s(I)]
R indices (all data)
R1 ¼ 0.0332
wR2 ¼ 0.0685
R1 ¼ 0.0448
wR2 ¼ 0.0716
0.938
4.4. Synthesis of palladacycles 3(aed)
A suspension of palladium chloride (0.5 mmol, 86.7 mg) and
sodium chloride (1 mmol, 58.5 mg) in methanol (20 mL) was stirred
at room temperature, until a brown homogeneous solution was
GoF(F2)
Absorptions corrections
Semi-empirical from equivalents